Molecular weight control in (NPCl{11 ){11 {11 polymerization

ABSTRACT

The molecular weight of the (NPCl2) polymer produced from the thermal polymerization of chlorocyclophosphazene trimer and/or tetramer or mixtures of trimer and tetramer is controlled by conducting the polymerization in the presence of controlled amounts of PCl5.

United States Patent Allcock et al.

Nov. 4, 1975 MOLECULAR WEIGHT CONTROL IN (NPCl POLYMERIZATION Inventors: Harry Rex Allcock; James Earl Gardner, both of State College, Pa.

The Firestone Tire & Rubber Company, Akron, Ohio Filed: Apr. 11, 1973 Appl. No.: 350,219

Published under the Trial Voluntary Protest Program on January 28, 1975 as document no. B 350,219.

Assignee:

US. Cl. 423/300; 260/2 P Int. Cl. C01B 25/10; COlB 21/52 Field of Search 260/2 P; 423/300 Primary ExaminerWilbert J. Briggs, Sr.

[ ABSIRACT The molecular weight of the (NPCl polymer produced from the thermal polymerization of chlorocyclophosphazene trimer and/or tetramer or mixtures of trimer and tetramer is controlled by conducting the polymerization in the presence of controlled amounts of PCI 3 Claims, N0 Drawings MOLECULAR WEIGHT CONTROL IN (N PCl2) n POLYMERIZATION NCi P Cl TABLE-continued Effect of PCl on the Polymerization of (NPC\)3 after 24 Hours at 250C Moles PCl l00 Relative Moles Appearance of Products Solution (NPCh); Product Vrscos|ty* fluid oligomers 1.4 Heterogeneous Cyclics and linear L03 fluid oh omers 0.09 gqrgogeneous Po ymer (NPCIQ: 1.3

m 0.006 Viscous Polymer (NPClz): 1.6

fluid 0 Very viscous Polymer L8 fluid or elastomer Relative solution viscosity is indicative of the degree of polymerization.

While not wishing to be bound by any specific theory as to how the PCl functions in the polymerization mixture, it appears that phosphorus pentachloride can function both as a chain termination agent and as a ring or chain cleavage agent. For example, the reaction of PCl with a cyclic phosphazene may proceed as follows:

PCK PC1 N PCQlS where n may be as high or higher than 5,000. A similar reaction occurs with the tetramer. No method is presently known by which the molecular weight of the polymer can be controlled by simple variation in the temperature, polymerization time, or pressure in the polymerization vessel.

In the presence of PCl the nature of the resulting product can be varied according to the amount of PCl present in the polymerization mixture. This is illustrated by the results set forth in the table below, the data having been obtained by the following experimental procedure.

Hexachlorocyclotriphosphazene was purified by sulfuric acid extraction from heptane solution, followed by precipitation onto ice, three recrystallizations from heptane, and two vacuum sublimations. A cooled sam- ,ple of this material g) was degassed in a constricted thick walled glass tube after addition of a weighed amount of phosphorus pentachloride. The evacuated tube was sealed, the contents were melted and mixed, and the tube was placed in a thermo-regulated oven at 250C for 24 hours. After completion of the reaction, the product in each tube was analyzed by 31, NMR spectroscopy, by solution viscosity techniques, and by gel permeation chromatography.

TABLE Effect of PCl, on the Polymerization Reaction of PCl with a chain apparently leads to a similar type of cleavage.

Thus, the number of chains present in the final reaction mixture will depend on the number of PCl molecules present. The fewer PCl molecules present, the longer will be the chains.

It is preferred to use from 0.25 moles to l X 10" moles of PCI,, per mole of chlorocyclophosphazene trimer or tetramer, and to conduct the polymerization at temperatures ranging from 200C to 300C for times as described in U.S. Pat. No. 3,370,020.

Having now described a preferred embodiment of the invention, it is not intended that it be limited except as may be required by the appended claims.

We claim:

1. In the polymerization of chlorocyclophosphazenes to produce a linear polymer (NPCI product in which n is from about 16 to about 20,000, wherein the polymerization of cyclo trimer, tetramer or mixtures thereof is conducted at temperatures of between 200 and 300C, the improvement which comprises: maintaining an amount of PCl between 0.25 moles and l X 10 moles of PCl per mole of chlorophosphazene, present with said chlorophosphazene and conducting the polymerization in the presence of said amount of PCI 2. The process of claim 1 wherein the chlorocyclophophazene is substantially all trimer and the temperature is about 250C.

3. The process of claim 1 wherein the chlorocyclophophazene is a mixture of trimer and tetramer. 

1. IN THE POLYMERIZATION OF CHLOROCYLOPHAZINES TO PRODUCE A LINER POLYMER (NPCL2)N PRODUCT IN WHICH N IS FROM ABOUT 16 TO ABOUT 20,000, WHEREN THE POLYMERIZATION OF CYCLO TRIMER, TETRAMER OF MIXTURES THEREOF IS CONDUCTED AT TEMPERATURES OF BETWEEN 200* AND 300*C, THE IMPROVEMENT WHICH COMPRISES MAINTAINING AN AMOUNT OF PCL3 BETWEEN 0.25 MOLES AND 1X10**-5 MOLES PF PCL3 PER MOL OF CHLOREPHOSPHAZENE. PRESENT WITH SAID CHLOROPHOSPHAZENE AND CONDUCTING THE POLYMERIZATION IN THE PRESENCE OF SAID AMOUNT OF PCL5.
 2. The process of claim 1 wherein the chlorocyclophophazene is substantially all trimer and the temperature is about 250*C.
 3. The process of claim 1 wherein the chlorocyclophophazene is a mixture of trimer and tetramer. 